Chalcogen-Based Aerogels As Sorbents for ... - ACS Publications

Article pubs.acs.org/est

Chalcogen-Based Aerogels As Sorbents for Radionuclide Remediation Brian J. Riley,*,† Jaehun Chun,† Wooyong Um,† William C. Lepry,† Josef Matyas,† Matthew J. Olszta,† Xiaohong Li,† Kyriaki Polychronopoulou,‡ and Mercouri G. Kanatzidis‡ †

Pacific Northwest National Laboratory, Richland, Washington 99352, United States Department of Chemistry, Northwestern University, Evanston, Illinois 60208, United States

‡

S Supporting Information *

ABSTRACT: The efficient capture of radionuclides with long half-lives such as technetium-99 (99Tc), uranium-238 (238U), and iodine-129 (129I) is pivotal to prevent their transport into groundwater and/or release into the atmosphere. While different sorbents have been considered for capturing each of them, in the current work, nanostructured chalcogen-based aerogels called chalcogels are shown to be very effective at capturing ionic forms of 99 Tc and 238 U, as well as nonradioactive gaseous iodine (i.e., a surrogate for 129I2), irrespective of the sorbent polarity. The chalcogel chemistries studied were Co0.7Bi0.3MoS4, Co0.7Cr0.3MoS4, Co0.5Ni0.5MoS4, PtGe2S5, and Sn2S3. The PtGe2S5 sorbent performed the best overall with capture efficiencies of 98.0% and 99.4% for 99Tc and 238 U, respectively, and >99.0% for I2(g) over the duration of the experiment. The capture efficiencies for 99Tc and 238U varied between the different sorbents, ranging from 57.3−98.0% and 68.1−99.4%, respectively. All chalcogels showed >99.0% capture efficiency for iodine over the test duration. This versatile nature of chalcogels can provide an attractive option for the environmental remediation of the radionuclides associated with legacy wastes from nuclear weapons production as well as wastes generated during nuclear power production or nuclear fuel reprocessing.

■

INTRODUCTION Aerogels are highly porous semisolids with many emerging applications. The most commonly studied types of aerogels are silica-based aerogels but other types have been pursued. One such type are nonoxide aerogels called chalcogels that are composed of chalcogen (S, Se, and/or Te)-based moieties and often have different properties than their oxide-based analogs.1 Chalcogels can be prepared through a few different methods including (1) thiolysis of alkoxides with H2S (e.g., GeSx),2 (2) condensation/agglomeration of nanoparticles (e.g., CdS, ZnS, CdSe, and PbS),3 or (3) chemical linkage of chalcogenide clusters with interlinking metals.4,5 Routes (1) and (2) pose limitations where route (1) typically requires the use of the highly toxic gas H2S and the compositions for route (2) are restricted to available nanoparticle chemistries. Route (3) is a more attractive option mainly because of the vast compositional flexibility. To date, Ge−S, Ge−Se, Sn−S, Sn−Se, Mo−S, W−S, and Fe−S precursor building blocks have been identified and these precursors undergo gelation when combined with one or more interlinking metal ions from a growing list that includes Bi3+, Co2+, Ni2+, Sb3+, Sn2+, and Zn2+.4−11 A key feature of chalcogels is that they can be used to selectively capture gaseous and ionic species, some of which may be desirable for separations and environmental remediation.4−12 This “built-in” selectivity, as it is best understood, is at least partially based on the affinity between the species of interest and the elementary building blocks of the chalcogels via © XXXX American Chemical Society

the chemical hardness (η, in eV) and the polarizability. Pearson’s Hard−Soft Acid−Base (HSAB) principle13−15 uses the chemical hardness of species to classify them as hard or soft Lewis acids or bases as η=

1 (I − A ) 2

(1)

where I is the ionization energy (in eV) and A is the electron affinity (in eV) of a species. This relation can be used to predict the affinity of any species of interest for another as long as these data are available. From eq 1, it can be determined that the chalcogens, S (η = 4.12 eV), Se (η = 3.86 eV), and Te (η = 3.52 eV), are soft Lewis bases.13 Some heavy metal ions are soft Lewis acids and tend to bind well to chalcogels showing potential for environmental remediation,4,10−12 for example, Hg2+ (η = 7.7 eV), Pb2+ (η = 8.5 eV), and Cd2+ (η = 10.3 eV).13 Also, chalcogels have been demonstrated to have a selective affinity for certain gases such as the ranking H2 < CH4 < CO2 < C2H6 for PtGeS and PtSbGeSe chalcogels, where the higher affinities were attributed to the more polarizable molecules.7 However, chalcogel affinity for radionuclides has never been explored until now while a limited study with nonradioactive Received: February 5, 2013 Revised: April 26, 2013 Accepted: May 17, 2013

A

dx.doi.org/10.1021/es400595z | Environ. Sci. Technol. XXXX, XXX, XXX−XXX

Environmental Science & Technology

Article

Table 1. Summary of Chalcogel Recipes chalcogel CoBiMoS (Co0.7Bi0.3MoS4) CoCrMoS (Co0.7Cr0.3MoS4) CoNiMoS (Co0.5Ni0.5MoS4) PtGeS (PtGe2S5) SnS (Sn2S3)

precursor 1 (g in mL)



solvent

gelation time (days)

Co(NO3)2·6H2O (3.34 g in 66 mL)

Bi(CH3COO)3 (1.27 g in 66 mL)

(NH4)2MoS4 (4.29g in 66 mL)

formamide

14

Co(NO3)2·6H2O (3.34 g in 66 mL)

Cr(NO3)3·9H2O (1.32 g in 66 mL)

(NH4)2MoS4 (4.29g in 66 mL)

formamide

12

CoCl2·6H2O (0.143 g in 7.5 mL)

Ni(NO3)2·6H2O (0.175 g in 7.5 mL)

(NH4)2MoS4 (0.312 g in 15 mL)

formamide

28

((CH3)4N))4Ge4S10 (1.09 g in 36 mL) Na4Sn2S6·14H2O (3.10 g in 80 mL)

K2PtCl4 (0.995 g in 24 mL) Sn(CH3COO)2 (1.89 g in 80 mL)

N/A N/A

DIW formamide

17 37

iodine was reported.11 This study evaluates the capture efficiency of chalcogels for technetium (99Tc), uranium (238U) and iodine. The target iodine is 129I evolved as a gaseous species (129I2(g)), although nonradioactive iodine was used in these studies. All three of these radionuclides are associated with legacy wastes (i.e., weapons production) as well as nuclear power production and nuclear fuel reprocessing. All of these have very long half-lives (t1/2) of 2.1 × 105 y (99Tc), 4.5 × 109 y (238U), and 1.6 × 107 y (129I) so their releases must fall below regulatory limits16,17 because they pose serious concerns toward public health in the event that they are leached into the groundwater and/or are released into the atmosphere.18,19 This has triggered significant research interest for the development of sorbents that can effectively and selectively capture these species out from the other species within their proximity, some of which might be nonhazardous. Both 99Tc and 129I are volatile and tend to leave as off-gases during high temperature processes such as vitrification for waste disposal or voloxidation for nuclear fuel reprocessing.20 The 99Tc will likely be reoxidized and converted to the pertechnetate anion (TcO4−) once being exposed to oxygen, so 99 Tc exists as TcO4− in solution at most pH conditions. The mobility of TcO4− in subsurface water is fairly significant; it would not be mitigated by sorption or solubility limitations.21 Several different types of sorbents have been investigated for capturing Tc that include ion-exchange materials,22 activated carbon,23 and natural minerals such as bentonite24 and goethite.18 On the other hand, 129I typically exists as iodide or iodate species upon introduction into aqueous solution. Due to the high vapor pressure and adverse health effects of gaseous iodine, the Environmental Protection Agency (EPA) regulation 40 CFR 190 requires more than 99.4 mass% for 129I capture and immobilization.16 Many different iodine sorbents have been identified that include chalcogels,11 silver-functionalized silica aerogels,25 apatite mineral structures,26 metal−organic frameworks,27 and monolithic aerogels of polymeric organic framework.28 The most prevalent iodine sorbent studied in the United States is a silver-exchanged zeolite (AgZ), while the Japanese and Europeans have studied AgNO3-impregnated alumina and silica.29 The AgZ and AgNO3-impregnated sorbents require silver to bind I2(g) but have an advantage in that they can be prepared in large volumes. The most prevalent form of U in the legacy waste is the hexavalent form (i.e., uranyl or UO22+).19 While UO2(OH)2o, UO2(OH)3−, and UO2(CO3)22‑ species are dominant with increasing pH in solution within the presence of the carbonate ion,30 UO22+ exists under oxidizing conditions and is considered as stable ionic form of U under low pH conditions.31 Some of the U sorbents that have been studied include silica gels,32 activated carbon-silica aerogel composite

materials,33 and partially sintered silica aerogels.34 Additionally, work has been done with a porous metal sulfide, K2MnSn2S6 (KMS-1) looking to capture U from seawater where the capture mechanism is believed to be an ion exchange process where UO22+ ions substitute into the crystal structure for the K+ ions.35 The purpose of the current study was to extend the previous sorbent work11 with chalcogels to study their efficacy for radionuclides. In this study, five different chalcogel chemistries were evaluated for capture of 10−6 M UO22+, 10−6 M TcO4−, and 4.2 ppm iodine gas (by volume). The chalcogel chemistries studied were Co0.7Bi0.3MoS4 (CoBiMoS), Co0.7Cr0.3MoS4 (CoCrMoS), Co0.5Ni0.5MoS4 (CoNiMoS), PtGe2S5 (PtGeS), and Sn2S3 (SnS).

■

EXPERIMENTAL SECTION 2.1. Chalcogel Fabrication. All chalcogels were prepared with techniques discussed in the literature.4,6,7,9,11 For each chalcogel, different chemical precursors were dissolved separately in a solvent (i.e., deionized water (DIW) or formamide), mixed together, and left to gel over a period of time (Table 1). The Na4Sn2S6·14H2O precursor for making the SnS chalcogel was prepared as shown in previous studies10,36 with Na2S·9H2O and SnCl4·5H2O as starting materials. The ((CH3)4N)4Ge4S10 precursor for the PtGeS chalcogel was prepared in a hydrothermal reaction according to literature procedures with (CH 3 ) 4 NOH, Ge, and S as starting materials. 11,37 The Bi(CH 3 COO) 3 , Co(NO 3 ) 2 ·6H 2 O, CoCl2·6H2O, Cr(NO3)3·9H2O, K2PtCl4, (NH4)MoS4, Ni(NO3)2·6H2O, and Sn(CH3COO)2 precursors were purchased commercially (see Table S1 in the Supporting Information (SI) for the purity and vendor of each chemical precursor). For each chalcogel, the individual precursors were added to solvents in separate beakers and stirred until the precursors were dissolved. Then, they were combined, stirred for a few minutes, and cast into either glass or polypropylene vials with lids and left to undergo gelation. Following gelation, the chalcogels were removed from their vials and diced into smaller pieces (∼ 1−5 mm in size) that we call “granules”. All chalcogels were placed into either pure ethanol or a mixture of ethanol and DIW to undergo aging for 1−3 days (see Table S2 in the SI). The aging process was followed by several rinses in a fresh solution of DIW (for PtGeS) or a mixture of ethanol and DIW (all except PtGeS) to remove the water-soluble byproducts of the chemical reactions. This was followed by several washes in 100% ethanol to remove the water. Then, the gels were washed several times with fresh liquid CO2 in an autoclave to remove the ethanol. Following the rinsing with liquid CO2, the vessel was heated to take the CO2 supercritical at which point the CO2 was slowly vented as a gas. B



Article

Figure 1. A schematic of the experimental setup for iodine gas uptake test in flowing air containing I2(g) at 4.2 ppm (a) and a photograph of a CoNiMoS chalcogel (black) in the bottom of the pipet prior to an experiment (b).

highlighted the ∼500−700 nm diameter region) with the diffraction pattern focused at the same plane as the objective aperture for consistency. 2.3. Tc and U Capture. For the 99Tc and 238U sorption experiments, masses of ∼0.05−0.1 g of the five different chalcogel chemistries were added to separate vials containing 9 mL of DIW (Table S3, SI). In addition, a “blank” sample was also prepared under the same conditions with 9 mL of DIW in a vial without any chalcogel sorbent to monitor radionuclides removal by the vials. Then, 1 mL of a stock solution containing either 10−5 M 99Tc (TcO4− added as NaTcO4) or 10−5 M 238U (UO22+ added as UO2(NO3)2) in DIW was added to the 9 mL vial for a final concentration of 10−6 M for each radionuclide. These samples were mixed in the vials for 7 days with an endover-end rotator and the supernatant was collected after separation of solution with 0.45 μm syringe filter. The concentration of either 99Tc or 238U in solution after 7 days was measured with inductively coupled plasma mass spectrometry (ICP-MS). The capture efficiency, based on the fraction removed, was calculated with eq 2 where Co was the initial mass concentration of the radionuclide (99Tc or 238U) and Cf was the final mass concentration of each radionuclide in chalcogel samples after 7 days. Also, the Kd (distribution coefficient) values were determined by comparing the concentrations of 99Tc or 238U between initial and final chalcogel samples as shown in eq 3 where V = 10 mL and m was the mass (g) of chalcogel sample used (Table S3, SI).

In a separate experiment, a series of SnS gels were prepared with the same procedure as those previously described but were not dried with supercritical CO2. Instead, the ethanol at the final solvent exchange step was intentionally allowed to evaporate, collapsing the pore structure. The product of this experiment was a SnS xerogel with significantly reduced surface area as compared to the aerogel. 2.2. Characterization. Prior to any uptake experiments, the chalcogels were characterized with a number of different techniques that included specific surface area measurements, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and selected area diffraction (SAD). Specific surface areas were measured for all of the chalcogels with N2(g) adsorption and desorption isotherms collected with a Quantachrome Autosorb-6B (Quantachrome Instruments, Boynton Beach, FL) gas sorption system on degassed samples. Samples were loaded in a glass sample holder and degassed at different temperatures (25−125 °C) while under vacuum. The degassed samples were analyzed with nitrogen adsorption and desorption at a constant temperature of 77.4 K (−195.75 °C), the temperature of liquid nitrogen. The specific surface areas were determined from the isotherm with the Brunauer− Emmett−Teller (BET) method.38 The Barrett−Joyner− Halenda (BJH) method was also used for the porosity and pore size analyses.39 In order to relate the surface area of the chalcogels to the more common silica aerogels, the “silica equivalent specific surface area” (SSAeq) was calculated.5 Here, the chalcogel composition was normalized to SiO2 having 2 oxygens. For example, Sn2.00S3.00 becomes Sn1.33S2.00 and the molecular mass of this compound (222.41 g/mol) is compared to that of SiO2 (60.08 g/mol) and the silica equivalent specific surface area translates to 3.70 times the values measured with the isotherms. Uncoated chalcogels were analyzed with a JSM-7001F SEM (JEOL USA, Inc., Peabody, MA) in Gentle Beam mode at low acceleration voltage (0.3 kV). Additionally, all chalcogels were analyzed with TEM and SAD with a JEOL 2010F operated at 200 kV with a 50 μm diameter condenser aperture. Powders of each sample were passed through a 325 μm mesh sieve, dispersed in isopropanol, and crushed in an agate mortar and pestle. Lacey carbon copper grids were then passed through the solution to collect fine particles and the grid was allowed to dry. Regions of interest were identified at electron transparent edges of the crushed powders as to not induce phase separation through beam damage. Bright field and diffraction images were collected from each sample. The microscope was calibrated in diffraction mode with the objective aperture as a physical constant and subsequent selected area diffraction on the aerogels was performed with a selected area aperture (which

%efficiency = 100 × (Co − Cf )/Co

(2)

Kd = V /m × ((Co − Cf )/Cf )

(3)

2.4. Iodine Gas Capture. A schematic of the experimental setup used for the iodine capture experiments is shown in Figure 1 (more details are presented elsewhere25). In this apparatus, air was flowed through a column into an oven at 100 °C and then through a DYNACAL iodine permeation tube with a permeation rate of 22.8597 ng s−1, equating to 4.2 ppm (by volume) I2(g) in air. The column transported this mixture of air/I2(g) into a second oven at 125 °C where the sample holder, a 10 mL glass pipet, was attached to the column. After passing through the pipet, either empty or containing the sorbent, the gas mixture was bubbled through a 0.1 M NaOH scrubber solution in DIW. Calibration runs were performed without a sorbent in the sample holder to determine the flow rate of I2(g) through the column. During the test, the scrubber solution was periodically removed and replaced with a fresh solution. Then, 20 mL aliquots were analyzed with ICP-MS and the iodine evolution rate was determined in the form of μg L−1 s−1. C



Article

during heating by desorption of residual solvent. The other three chalcogels (CoNiMoS, PtGeS, and SnS) were analyzed as granules and the general trend was a decrease in specific surface area with increased degas temperatures. This can be attributed to additional pore collapse during heating due to the evaporation of residual solvent; it was fairly difficult to remove all of the solvent during the solvent exchange procedure as was evidenced by minor volumetric reduction of all granules in the weeks following the supercritical CO2 drying process. 3.2. Tc and U Capture. The sample mass, final solution pH, and solution color varied for each experiment as presented in Figure 3 and the SI. It should be noted that no significant removal (99% for iodine gas over the duration presented. The MoCoNiS chalcogel showed some breakthrough after the 4 h time point, where uncaptured iodine was measured in the scrubber solution. The reason for this remains unclear. Note that only the SnS chalcogel had a capture efficiency greater than that required to meet the EPA guideline of ≥99.4% for the entire duration of the experiment.16 The SnS xerogel had a specific surface area of 0.14 m2/g, more than 3 orders of magnitude less surface area than the compositionally equivalent SnS aerogel (456 m2/g) but, surprisingly, showed measurable capture efficiency (Figure 4b). Such appreciable capture efficiency of the xerogel clearly supports the postulation that the affinity between I2(g) and S

Then, 1−5 mL of chalcogel granules were lightly packed into the sample holder and connected to the apparatus in the oven at 125 °C for several hours. The scrubber solutions were collected at different evolution times and analyzed with ICPMS to determine the concentration of iodine in the sample (Cs). The breakthrough iodine from the experiments with the sorbent in the column was compared to the calibration runs and the capture efficiency of the sorbent was determined with eq 4 where Cc was the iodine concentration calculated from the calibration runs (without sorbent) for the same evolution time.

■

%efficiency = 100 × (Cc − Cs)/Cc

(4)

RESULTS AND DISCUSSION 3.1. Chalcogel Characterization. The basic microstructure of the SnS chalcogel as observed with SEM is shown in Figure 2. The structure as observed with TEM is

Figure 2. SEM and TEM micrographs of the chalcogels. Insets are SAD patterns showing diffuse scattering consistent with the nonperiodic nature of the chalcogels.

presented in Figure 2 and shows noticeably different morphologies between the various chalcogels. The CoBiMoS, CoCrMoS, and CoNiMoS chalcogels looked similar to one another with more dense networks, while the SnS chalcogel showed a more dispersed network and the PtGeS was highly porous. The SAD analysis on representative chalcogel granules showed amorphous structure (Figure 2). Some crystalline diffraction was observed with SnS and is presumed to be surface oxidation as evidenced by white discoloration on the surface of the granules. The specific surface areas varied significantly with chemistry and, for some of the chalcogels, it also moderately varied with degas temperatures (see Table 2). The CoBiMoS and CoCrMoS chalcogels were tested as powders and it is likely that all of the solvent was removed during the supercritical drying process so the specific surface area was not altered D



Article

Table 2. Summary of Specific Surface Area (SSA, m2/g) Measurements, The Calculated Silica Equivalent Surface Area (SSAeq, in Parentheses), and Pore Volume (cm3/g) for the Various Chalcogels Collected at Different Degassing Temperatures (Td) 25 °C 2

SSA, m /g (SSAeq, m /g)

CoBiMoS

251 (685) 118 (276) 582 (1371) 423 (1410) 456 (1688)

CoNiMoS PtGeSa SnS a

Vpore (cm /g)

2

Td = chalcogel

CoCrMoS

60 °C 3

2

SSA, m /g

100 °C 3

Vpore (cm /g)

2

3.0 3.1 3.9

Vpore (cm /g)

1.1

3.3 3.4 3.5

SSA, m /g

Vpore (cm3/g)

(SSAeq, m /g)

255 (696) 130 (304) 551 (1298) 418 (1393) 378 (1399)

0.77

2

2

(SSAeq, m /g)

257 (702) 127 (297) 580 (1366) 491 (1636) 432 (1599)

0.69

SSA, m /g

125 °C 3

2

(SSAeq, m /g) 1.2

2

1.1

252 (688) 132 (309) 503 (1185) 428 (1426) 364 (1347)

0.68 2.6 2.9 3.0

0.99 0.78 2.2 3.0 2.2

This is data from a different, but identically made and processed, PtGeS sample, presented in our earlier work.11

Figure 3. Pictures of vials containing the various chalcogels in 10 mL of DIW (colors representative of the 238U experiments).

would be a more decisive factor for effective capture than the surface area of a chalcogel. 3.4. Capture Mechanism. Figure 5 shows an inverse relationship between the available surface area and the capture efficiency for the 99Tc and 238U experiments, where the “available surface area” is the product of (1) the sorbent mass added to each solution and (2) the specific surface area (see Table 2 and Table S3 in the SI). The data show a somewhat counterintuitive trend based on a simple rationale for adsorption where the quantity of adsorbed species should be proportional to the available binding sites. Figure 5 suggests that the available surface area and pore volume might not be as critical to maximize the binding efficiency as was previously thought. The fact that the degrees of the inverse correlation differ from the sorbates would also support this rationale. Furthermore, as pointed out, the polarity also cannot explain the trend across different pH values (Table 2). Regarding iodine capture, all of the chalcogels studied here showed comparably high capture efficiencies. It is known that I2(g) is a soft Lewis acid (η = 3.4 eV)11 and since the only common chemistry link between the three sorbents tested is Table 3. Summary of 99Tc and

Figure 4. Iodine uptake results for (a) three of the aerogels and (b) a SnS xerogel. Data for PtGeS was extracted from Riley et al.11.

238

U Uptake with Various Chalcogels 99

238

Tc-uptake

sample ID

eff. (%)

CoBiMoS CoCrMoS CoNiMoS PtGeS SnS Blank

94.0 57.3 62.2 98.0 87.3

Kd (mL/g)

final pH

color

eff. (%)

× × × × ×

2.31 2.78 4.12 4.80 5.47 5.59

very blue faintly pink pale blue faintly orange faint yellow clear

94.9 68.1 88.2 99.4 99.1

1.68 2.88 1.62 3.61 1.49

103 102 102 104 103

E

U-uptake

Kd (mL/g)

final pH

color

× × × × ×

2.26 2.72 9.06 4.44 5.53 5.18

faintly blue barely pinkish pale blue faintly orange faintly yellow clear

1.81 3.15 8.08 9.43 2.31

103 102 102 104 104



Figure 5. Comparison of capture efficiency (%) for versus available surface area for all chalcogels.

Article

238

U and

efficiencies for various radionuclides with all polarities as discussed here implies that chalcogels can be potentially considered as a versatile sorbent in many different applications where the species of interest is a soft acid or more polarizable than the surrounding secondary species. For example, chalcogels would be a candidate sorbent as a backfill barrier material in underground radioactive waste repositories to prevent potential leaching of radioactive contaminants because of their inherent high capture capacity for different phases of radioactive contaminants. One concern with these sorbents is the toxicity associated with some of the chalcogel constituents such as Se, Te, Pb, and Cr, a few of which are controlled by the EPA under the Resource Conservation and Recovery Act.52 However, many chalcogel chemistries do not include these toxic elements. Also, some of these compounds show moderate to high air sensitivity that has been observed to increase with the progression S → Se → Te. However, with a few exceptions,9 most of the research to date shows that sulfide-based chalcogels are quite stable in air and when submersed in water. Additionally, research is currently underway to assess the difference between the binding affinity of S- and Se-based chalcogels of like chemistry for iodine and the details of that study will be presented in a subsequent paper.

99

Tc

the chalcogen backbone, this seems to suggest a similar binding mechanism between the sorbents and supports the HSAB principle theory. While the UO22+ ion has been assumed to be a hard Lewis acid, a recent study strongly suggested that the UO22+ ion is indeed much softer.35 The conventional thinking regarding this ion is that it is a hard ion (hard Lewis acid) because the U is in the 6+ oxidation state. The two double bonds to the oxide ions (OUO), however, considerably soften the U center and cause it to behave more like a lead ion, providing evidence to support the HSAB principle binding theory. However, while chalcogels do show a selective affinity for softer acids and more polarizable species,4−10 based on the wide range of capture efficiencies with the 99Tc and 238U experiments, the HSAB principle alone might not be adequate to explain the binding mechanism for these species. That is because it suggests that the chalcogens, alone, are responsible for binding the species of interest. This warrants further investigations that are currently underway. 3.5. Additional Applications. In addition to the species discussed here (i.e., Hg2+, Pb2+, and Cd2+), chalcogels have been demonstrated to capture other, nonradioactive species4,10,12 such as Fe2+ (η = 7.3 eV) and Cu2+ (η = 8.3 eV).13 Based on the HSAB principle as a predictive tool, other soft Lewis acids that could be of interest in ionic form include Pu3+ (η = 6.5 eV),43 Am3+ (η = 7.05 eV),43 Tl+ (η = 7.2 eV),13 U4+ (η = 7.4 eV),44 and Ni2+ (η = 8.5 eV),13 some of which are radioactive. Additionally, noble gases evolved in the off-gas during nuclear fuel reprocessing45 could, in theory, be selectively captured with chalcogels based on their high polarizabilities (α, × 10−24 cm3), i.e., 85Kr (α = 2.484) and Xe (α = 4.044),46,47 as compared to the lower polarizabilities of the surrounding species, that is, N2 (α = 1.74),46,48 NO (α = 1.7),49 O2 (α = 1.57),50 and H2 (α = 0.81).46 However, this would likely require subambient or even cryogenic temperatures, which might prove difficult to implement in a reprocessing facility. One of the other gaseous species of interest evolved during reprocessing is 14C in the form of 14 CO2, which has a high polarizability (α = 2.91),51 is considered a soft Lewis acid (η = 6.9 eV),13 and has been demonstrated to adsorb to Pt-based chalcogels7 as was discussed previously. 3.6. Environmental Implications of Chalcogels Sorbents. Our study clearly indicated that chalcogels assembled with various building blocks can be used to remove gaseous iodine (or radioactive 129I) and aqueous radionuclides (99Tc and 238U). Furthermore, the wide range of high capture

■

ASSOCIATED CONTENT

* Supporting Information S

Experimental details regarding the chemicals used to fabricate the chalcogels in this study as well as the parameters for aging, solvent exchange, and supercritical drying. This material is available free of charge via the Internet at http://pubs.acs.org/.

■

AUTHOR INFORMATION

Corresponding Author

*Phone: (509) 372-4651; e-mail: [email protected]. Notes

The authors declare no competing financial interest.

■

ACKNOWLEDGMENTS The Pacific Northwest National Laboratory is operated by Battelle under Contract Number DE-AC05-76RL01830. Authors thank John McCloy and Denis Strachan for helpful review of this document. We thank Naoki Kikuchi at JEOL Ltd. for providing SEM micrographs of the uncoated chalcogels. This work was funded in part by the Department of Energy Office of Nuclear Energy and in party by an internal Laboratory-Directed Research and Development project. A portion of this research was supported by WCU (World Class University) program at Pohang University of Science and Technology (POSTECH) through the National Research Foundation of Korea funded by the Ministry of Education, Science, and Technology (R31-30005). Research on chalcogels and radionuclide capture at Northwestern University is funded by the Department of Energy’s Nuclear Energy University Partnership program.

■

REFERENCES

(1) Kanatzidis, M. G. Beyond silica: nonoxidic mesostructured materials. Adv. Mater. 2007, 19 (9), 1165. (2) Kalebaila, K. K.; Georgiev, D. G.; Brock, S. L. Synthesis and characterization of germanium sulfide aerogels. J. Non-Cryst. Solids 2006, 352 (3), 232.

F



Article

(25) Matyás,̌ J.; Fryxell, G. E.; Busche, B. J.; Wallace, K.; Fifield, L. S. In Ceramic Engineering and Science: Ceramic Materials for Energy Applications; Lin, H.-T., Katoh, Y., Fox, K. M., Belharouak, I., Widjaja, S., Singh, D., Eds.; Wiley-The American Ceramic Society: Daytona Beach, FL, 2011; Vol. 32, p 23. (26) Watanabe, Y.; Ikoma, T.; Yamada, H.; Suetsugu, Y.; Komatsu, Y.; Stevens, G. W.; Moriyoshi, Y.; Tanaka, J. Novel Long-Term Immobilization Method for Radioactive Iodine-129 Using a Zeolite/ Apatite Composite Sintered Body 2009, 1 (7), 1579. (27) Sava, D. F.; Rodriguez, M. A.; Chapman, K. W.; Chupas, P. J.; Greathouse, J. A.; Crozier, P. S.; Nenoff, T. M. Capture of volatile iodine, a gaseous fission product, by zeolitic imidazolate framework-8. J. Am. Chem. Soc. 2011, 133 (32), 12398. (28) Katsoulidis, A. P.; He, J.; Kanatzidis, M. G. Functional monolithic polymeric organic framework aerogel as reducing and hosting media for Ag nanoparticles and application in capturing of iodine vapors. Chem. Mater. 2012, 24 (10), 1937. (29) Haefner, D. R.; Tranter, T. J. Methods of Gas Phase Capture of Iodine from Fuel Reprocessing Off-Gas: A Literature Survey, INL/EXT07-12299; Idaho National Laboratory, 2007. (30) Um, W.; Mattigod, S.; Serne, R.; Fryxell, G.; Kim, D.; Troyer, L. Synthesis of nanoporous zirconium oxophosphate and application for removal of U(VI). Water Res. 2007, 41 (15), 3217. (31) Ryan, J.; Buck, E.; Chun, J.; Crum, J.; Riley, B.; Strachan, D.; Sundaram, S.; Turo, L.; Vienna, J. Alternate Waste Forms: Aqueous Processing, AFCI-WAST-PMO-MI-DV-2009-000360; Pacific Northwest National Laboratory: Richland, WA, 2009. (32) Michard, P.; Guibal, E.; Vincent, T.; Le Cloirec, P. Sorption and desorption of uranyl ions by silica gel: pH, particle size and porosity effects. Microporous Mater. 1996, 5 (5), 309. (33) Coleman, S. J.; Coronado, P. R.; Maxwell, R. S.; Reynolds, J. G. Granulated activated carbon modified with hydrophobic silica aerogelpotential composite materials for the removal of uranium from aqueous solutions. Environ. Sci. Technol. 2003, 37 (10), 2286. (34) Woignier, T.; Reynes, J.; Phalippou, J.; Dussossoy, J. L.; JacquetFrancillon, N. N. Sintered silica aerogel: a host matrix for long life nuclear wastes. J. Non-Cryst. Solids 1998, 225 (1), 353. (35) Manos, M. J.; Kanatzidis, M. G. Layered metal sulfides capture uranium from seawater. J. Am. Chem. Soc. 2012, 134 (39), 16441. (36) Krebs, V. B.; Pohl, S.; Schiwy, W. Darstellung und Struktur von Na4Ge2S6·14H2O und Na4Sn2S6·14H2O. Z. Anorg. Allg. Chem. 1972, 393 (3), 241. (37) Bowes, C. L.; Huynh, W. U.; Kirkby, S. J.; Malek, A.; Ozin, G. A.; Petrov, S.; Twardowski, M.; Young, D. Dimetal linked open frameworks: [(CH3)4N]2(Ag2,Cu2)Ge4S10. Chem. Mater. 1996, 8 (8), 2147. (38) Brunauer, S.; Emmett, P. H.; Teller, E. Adsorption of gases in multimolecular layers. J. Am. Chem. Soc. 1938, 60 (2), 309. (39) Gregg, S.; Sing, K. Adsorption, Surface Area, And Porosity; 2nd ed.; Academic Press: Orlando, 1982. (40) Preetha, C. R.; Gladis, J. M.; Rao, T. P.; Venkateswaran, G. Removal of toxic uranium from synthetic nuclear power reactor effluents using uranyl ion imprinted polymer particles. Environ. Sci. Technol. 2006, 40 (9), 3070. (41) Walter, M.; Arnold, T.; Reich, T.; Bernhard, G. Sorption of uranium(VI) onto ferric oxides in sulfate-rich acid waters. Environ. Sci. Technol. 2003, 37 (13), 2898. (42) Um, W.; Serne, R.; Krupka, K. Surface complexation modeling of U(VI) adsorption to Hanford sediment with varying geochemical conditions. Environ. Sci. Technol. 2007, 41 (10), 3587. (43) Cotton, S. Lanthanide and Actinide Chemistry, Inorganic Chemistry: A Textbook Series; John Wiley & Sons, Ltd.: West Sussex, 2006. (44) Pyper, N. C.; Grant, I. P. Studies in multiconfiguration DiracFock theory III. Interpretation of the electronic structure of neutral and ionized states of uranium. J. Chem. Soc., Faraday Trans. 2 1978, 74 (11), 1885. (45) Paviet-Hartmann, P.; Kerlin, W.; Bakhtiar, S. Treatment of Gaseous Effluents Issued from RecyclingA Review of the Current

(3) Mohanan, J. L.; Arachchige, I. U.; Brock, S. L. Porous semiconductor chalcogenide aerogels. Science 2005, 307 (5708), 397. (4) Bag, S.; Trikalitis, P. N.; Chupas, P. J.; Armatas, G. S.; Kanatzidis, M. G. Porous semiconducting gels and aerogels from chalcogenide clusters. Science 2007, 317 (5837), 490. (5) Kanatzidis, M. G.; Bag, S. Semiconducting aerogels from chalcogenido clusters with broad applications, U.S. patent 2008/ 0241050 A1, Northwestern University, 2008, p 10. (6) Bag, S.; Gaudette, A. F.; Bussell, M. E.; Kanatzidis, M. G. Spongy chalcogels of non-platinum metals act as effective hydrodesulfurization catalysts. Nat. Chem. 2009, 1 (3), 217. (7) Bag, S.; Kanatzidis, M. G. Chalcogels: Porous metal-chalcogenide networks from main-group metal ions. Effect of surface polarizability on selectivity in gas separation. J. Am. Chem. Soc. 2010, 132 (42), 14951. (8) Shafaei-Fallah, M.; Alexander, R.; Katsoulidis, A. P.; He, J.; Malliakas, C. D.; Kanatzidis, M. G. Extraordinary selectivity of CoMo3S13 chalcogel for C2H6 and CO2 adsorption. Adv. Mater. 2011, 23 (42), 4857. (9) Polychronopoulou, K.; Malliakas, C.; He, J.; Kanatzidis, M. Selective surfaces: Quaternary Co(Ni)MoS-based chalcogels with divalent (Pb2+, Cd2+, Pd2+) and trivalent (Cr3+, Bi3+) metals for gas separation. Chem. Mater. 2012, 24 (17), 3380. (10) Oh, Y.; Bag, S.; Malliakas, C. D.; Kanatzidis, M. G. Selective surfaces: High-surface-area zinc tin sulfide chalcogels. Chem. Mater. 2011, 23 (9), 2447. (11) Riley, B. J.; Chun, J.; Ryan, J. V.; Matyás,̌ J.; Li, X. S.; Matson, D. W.; Sundaram, S. K.; Strachan, D. M.; Vienna, J. D. Chalcogen-based aerogels as a multifunctional platform for remediation of radioactive iodine. RSC Adv. 2011, 1, 1704. (12) Pala, I. R.; Brock, S. L. ZnS nanoparticle gels for remediation of Pb2+ and Hg2+ polluted water. ACS Appl. Mater. Interfaces 2012, 4 (4), 2160. (13) Parr, R. G.; Pearson, R. G. Absolute hardness: companion parameter to absolute electronegativity. J. Am. Chem. Soc. 1983, 105 (26), 7512. (14) Pearson, R. G. Hard and soft acids and bases. J. Am. Chem. Soc. 1963, 85 (22), 3533. (15) Pearson, R. G. Chemical Hardness; Wiley-VCH Verlag GmbH: Weinheim, Germany, 1997. (16) Environmental Radiation Protection Requirements for Normal Operations of Activities in the Uranium Fuel Cycle, 40 CFR 190; Environmental Protection Agency: Washington, D.C., 2012. (17) Standards for Protection against Radiation, 10 CFR 20; United States Nuclear Regulatory Commission: Washington, D.C., 2012. (18) Um, W.; Chang, H.-S.; Icenhower, J. P.; Lukens, W. W.; Serne, R. J.; Qafoku, N. P.; Westsik, J. H.; Buck, E. C.; Smith, S. C. Immobilization of 99-technetium (VII) by Fe(II)-goethite and limited reoxidation. Environ. Sci. Technol. 2011, 45 (11), 4904. (19) Um, W.; Serne, R.; Wang, Z.; Brown, C.; Williams, B.; Dodge, C.; Francis, A. Uranium phases in contaminated sediments below Hanford’s U tank farm. Environ. Sci. Technol. 2009, 43 (12), 4280. (20) Wahlquist, D. L.; Bateman, K. J.; Westphal, B. R. Second generation experimental equipment design to support voloxidation testing at INL. In Proceedings of 16th International Conference on Nuclear Engineering; Vol. 2, p91. (21) Radioactivity in the Terrestrial Environment; Shaw, G., Ed.; Elsevier: Oxford, UK, 2007; Vol. 10. (22) Collins, J. L.; Egan, B. Z.; Anderson, K. K.; Chase, C. W.; Bell, J. T. In 2nd International Conference of Waste Management: Challenges and Innovations in the Management of Hazardous Waste, CONF-9505101-1; Washington, D.C., 1995; p 1. (23) Gu, B.; Dowlen, K. E.; Liang, L.; Clausen, J. L. Efficient separation and recovery of technetium-99 from contaminated groundwater. Sep. Technol. 1996, 6 (2), 123. (24) Kohlickova, M.; Jedinakova-Krizova, V.; Horejs, M. Influence of technetium and rhenium speciation on the sorption on natural sorbents. Czech. J. Phys. 1999, 49 (1), 695. G



Article

Practices and Prospective Improvements, INL/CON-10-19961; Idaho National Laboratory, 2010. (46) Orcutt, R. H.; Cole, R. H. Dielectric constants of imperfect gases. III. Atomic gases, hydrogen, and nitrogen. J. Chem. Phys. 1967, 46 (2), 697. (47) Miller, T. M.; Bederson, B. Atomic and molecular polarizabilitiesA review of recent advances, In Advances in Atomic and Molecular Physics; Bates, D. R., Benjamin, B., Eds.; Academic Press: New York, 1978; Vol. 13, p 1. (48) Newell, A. C.; Baird, R. C. Absolute determination of refractive indices of gases at 47.7 gigahertz. J. Appl. Phys. 1965, 36 (12), 3751. (49) Maryott, A. A.; Buckley, F. Circular of the Bureau of Standards: Table of Dielectric Constants and Electric Dipole Moments of Substances in the Gaseous State; U.S. Dept. of Commerce, National Bureau of Standards, 1953; Vol. 537. (50) May, E. F.; Moldover, M. R.; Schmidt, J. W. Electric and magnetic susceptibilities of gaseous oxygen: Present data and modern theory compared. Phys. Rev. A 2008, 78 (3), 032522. (51) Bose, T. K.; Cole, R. H. Dielectric and pressure virial coefficients of imperfect gases. II. CO2−argon mixtures. J. Chem. Phys. 1970, 52 (1), 140. (52) Identification and Listing of Hazardous Waste, CFR 261; Environmental Protection Agency: Washington, D.C., 2012; Vol. 40.

H


Chalcogen-Based Aerogels As Sorbents for ... - ACS Publications

Recommend Documents